Process for producing olefin terpolymers with bridged phenolate transition metal complexes

Patent metadata

Field	Value
Publication number	US-11168162-B2
Application number	US-201916597695-A
Country	US
Kind code	B2
Filing date	Oct 9, 2019
Priority date	Oct 23, 2018
Publication date	Nov 9, 2021
Grant date	Nov 9, 2021

Abstract

The present disclosure provides polymerization processes to produce polymeric materials, such as olefin terpolymers, using transition metal catalysts having bridged phenolate ligands. The polymerization process includes contacting a transition metal complex with a mixture olefin monomers that contain ethylene, propylene, and a cyclic diene to produce an olefin polymer and recovering the olefin polymer. The mixture of olefin monomers can include specified weight ratios for the various olefin monomers. The transition metal complex includes a bridged phenolate ligand bonded to a metal atom via covalent bonds by two oxygens, a coordinate covalent bond by a Group 15 atom, and a coordinate covalent bond by a Group 15 or 16 atom. The transition metal complex provides relatively high endocyclic alkene/vinyl selectivity to minimize hyperbranching during the production of olefin polymeric materials, such as EPDM and other terpolymers that are free or substantially free of gels.

First claim

What is claimed is:

1. A polymerization process to produce an olefin polymer, comprising:
A) contacting a transition metal complex with a mixture of olefin monomers comprising ethylene, propylene, and a cyclic diene to produce the olefin polymer, wherein the mixture of olefin monomers comprises:
a weight ratio of the ethylene to the cyclic diene of about 20:1 to about 500:1;
a weight ratio of the propylene to the cyclic diene of about 100:1 to about 1,000:1; and
a weight ratio of the propylene to the ethylene of about 1:1 to about 40:1; and

B) recovering the olefin polymer, wherein the olefin polymer has:
an ethylene content of about 40 wt % to about 85 wt %;
a propylene content of about 15 wt % to about 50 wt %;
a cyclic diene content of about 0.05 wt % to about 5 wt %; and
a g′( vis ) value of about 0.90 to 1; and

wherein the transition metal complex is represented by Formula (I):

wherein:
M is a Group 4 transition metal;
each X 1 and X 2 is independently a univalent C 1 to C 20 hydrocarbyl, a C 1 to C 20 substituted hydrocarbyl, a heteroatom, or a heteroatom containing group; or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
Q is a neutral donor group comprising a Group 15 atom or a Group 16 atom;
Y is a substituted or unsubstituted divalent C 1 -C 40 hydrocarbyl, or a substituted or unsubstituted heterocycle with Q;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 is independently a hydrogen, a C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, a heteroatom, or a heteroatom containing group; or two or more of adjacent R 1 to R 10 join together to form a C 4 to C 62 cyclic, polycyclic, heterocyclic ring, or a combination thereof;
J is a C 7 to C 60 fused polycyclic group; and
G is a hydrogen, C 7 to C 60 fused polycyclic group, a C 1 -C 60 hydrocarbyl, a C 1 -C 60 substituted hydrocarbyl, a heteroatom, or a heteroatom containing group; or forms a C 4 to C 60 cyclic or polycyclic ring with R 6 , R 7 , or R 8 , or a combination thereof.

2. The polymerization process of claim 1 , wherein the cyclic diene comprises an endocyclic alkene and a vinyl group.

3. The polymerization process of claim 1 , wherein the olefin polymer has a g′( vis ) value of about 0.95 to 1.

4. The polymerization process of claim 1 , wherein the olefin polymer has a g′( vis ) value of about 0.97 to 1.

5. The polymerization process of claim 1 , wherein the olefin polymer has a g′( vis ) value of about 0.98 to 1.

6. The polymerization process of claim 1 , wherein the olefin polymer has a Mooney viscosity ML (1+4) at 125° C. of about 20 MU to about 100 MU.

7. The polymerization process of claim 1 , wherein the olefin polymer has a Mooney viscosity ML (1+4) at 125° C. of about 30 MU to about 60 MU.

8. The polymerization process of claim 1 , wherein the olefin polymer has an MLRA of about 50 MU to about 200 MU.

9. The polymerization process of claim 1 , wherein the olefin polymer has an MLRA of about 100 MU to about 150 MU.

10. The polymerization process of claim 1 , wherein the cyclic diene comprises vinyl norbornene (VNB), ethylidene norbornene (ENB), dicyclopentadiene (DCPD), or any combination thereof.

11. The polymerization process of claim 1 , wherein the mixture of olefin monomers comprises:
a weight ratio of the ethylene to the cyclic diene of about 40:1 to about 200:1;
a weight ratio of the propylene to the cyclic diene of about 200:1 to about 500:1; and
a weight ratio of the propylene to the ethylene of about 2:1 to about 10:1.

12. The polymerization process of claim 1 , wherein the mixture of olefin monomers comprises:
a weight ratio of the ethylene to the cyclic diene of about 50:1 to about 100:1;
a weight ratio of the propylene to the cyclic diene of about 300:1 to about 400:1; and
a weight ratio of the propylene to the ethylene of about 3:1 to about 7:1.

13. The polymerization process of claim 1 , wherein the olefin polymer has:
an ethylene content of about 50 wt % to about 75 wt %;
a propylene content of about 25 wt % to about 40 wt %; and
a cyclic diene content of about 0.1 wt % to about 3 wt %.

14. The polymerization process of claim 1 , wherein the olefin polymer has:
an ethylene content of about 55 wt % to about 70 wt %;
a propylene content of about 28 wt % to about 38 wt %; and
a cyclic diene content of about 0.2 wt % to about 2 wt %.

15. The polymerization process of claim 1 , wherein the olefin polymer has:
an ethylene content of about 60 wt % to about 67 wt %;
a propylene content of about 30 wt % to about 35 wt %; and
a cyclic diene content of about 0.25 wt % to about 1 wt %.

16. The polymerization process of claim 1 , wherein M is Hf or Zr.

17. The polymerization process of claim 1 , wherein Q comprises O, S, N, or P.

18. The polymerization process of claim 1 , wherein Q comprises N or O.

19. The polymerization process of claim 1 , wherein Y is a divalent C 1 -C 20 hydrocarbyl.

20. The polymerization process of claim 1 , wherein Y is a divalent C 1 -C 5 hydrocarbyl.

21. The polymerization process of claim 1 , wherein G and J is independently carbazolyl, substituted carbazolyl, indolyl, substituted indolyl, indolinyl, substituted indolinyl, imidazolyl, substituted imidazolyl, indenyl, substituted indenyl, indanyl, substituted indanyl, fluorenyl, substituted fluorenyl, naphthyl, substituted naphthyl, anthracenyl, substituted anthracenyl, phenanthryl, or substituted phenanthryl.

22. The polymerization process of claim 1 , wherein the transition metal complex is represented by Formula (VI) or (VII):

wherein:
Y is a C 1 -C 3 divalent hydrocarbyl;
Q 1 is NR′ 2 , OR′, SR′, PR′ 2 , where R′ is as defined for R 1 ; or the -(-Q-Y—)— fragment forms a substituted or unsubstituted heterocycle ring; and
each X is independently benzyl, methyl, ethyl, chloride, bromide, or alkoxide.

23. The polymerization process of claim 22 , wherein R′ is methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, or linked together to form a five or six-membered ring.

24. The polymerization process of claim 1 , wherein the transition metal complex is represented by Formula (VIII):

wherein M is Zr or Hf.

25. The polymerization process of claim 1 , wherein the contacting includes contacting an activator, along with the transition metal complex, wherein the activator and the transition metal complex forms a catalyst system, with the mixture of olefin monomers.

26. The polymerization process of claim 25 , wherein the catalyst system further comprises a chain transfer agent.

27. The polymerization process of claim 26 , wherein the chain transfer agent comprises a C 1 -C 20 alkyl aluminum compound, a C 1 -C 20 alkyl zinc compound, or a combination thereof.

28. The polymerization process of claim 27 , wherein the chain transfer agent comprises a C 1 -C 5 alkyl aluminum compound, a C 1 -C 5 alkyl zinc compound, or a combination thereof.

29. The polymerization process of claim 26 , wherein the chain tran

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Atienza Crisita Carmen H
• Shah Rhutesh K

Classifications

• C08F4/659

  Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F4/64186

  Dianionic ligand · CPC title

• C08F210/18 Primary

  with non-conjugated dienes, e.g. EPT rubbers · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title